New vat dyestuffs



' No Drawing.

l atented Oct. 6, 1931 UNITED STATES PATENT QFFICE MAX ALBERT KUNZ, OF IJL'ANNHEIM, AND KARL K'OEBERLE, OF LUIDWIG-SEAFEN-ON- THE-RHINE, GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC., 01? NEW YORK, N. Y., A CORPORATION OF DELAWARE 7 NEW VAT DYESTUFFS mula wherein 'n is 1 or 2. The said new products are blue-violet powders dissolving in concentrated sulphuric acid to give red to blue red solutions and dye cotton from a brown red to blue red vat strong currant to violet red shades of excellent fasteness.

Those of the new condensation products according to the present invention, which are obtainable from 1 molecular proportion of a dihalogen 3.4.8.9 dibenzopyrene 5.10-quinone and 2 molecular proportions of alphaaminoanthraquinone, and in particular those derived from the dibromo-3.4.8.9-dibenzopyrene-5.10-quinone which is obtainable by dissolving 33 parts of pure 3.4.8.9-dibenzopyrene-5.10-quinone in 330 parts of chlorosulphonic acid, adding from 1.65 to 2.3 parts of iodine and then at room temperature parts of bromine, and heating to from to C. until the bulk of the bromine has been Application filed March 15, 1923. Serial No. 347,444.

taken up, the constitution of this product is I probably as follows:

ample with aluminum chloride or with a mixture of aluminum chloride and sodium chloride, formation of a carbazol nucleus takes place and new dyestufis are obtained which are only difficultly soluble in concentrated sulphuric acid with the formation of a blue solution and which dye the vegetable fibre from a violet vat very fast brown shades.

When the new condensation products corresponding to the above formula are treated with oxidizing agents in acid solution, for example with manganese dioxide in sulphuric acid, new dyestuffs are obtained which dye cotton from a violet vat strong grey shades and dissolve in concentrated sulphuric acid to a violet solution. When these dyestuffs are alkylated, for example, methylated, they are converted into products dyeing the vegetable fibre from red-violet vats dark blue shades.

The following examples will further illustrate the nature of the present invention which however is not limited thereto. The parts are by weight.

Ewample 1 98 parts of the dibromo-3.4.8.9-dibenzopyrene-5.10-quinone specifically referred to above in a finely divided state are boiled in 1500 parts of naphthalene, while stirring, with 100 parts of calcined sodium carbonate, 10 parts of copper oxide and 92 parts of alpha-aminoanthraquinone, until the reaction product is practically free from bromine. The mass is allowed to cool to about 180 to 140 C. and diluted with 1500 parts of monochlorobenzene. The reaction product is filtered by suction and treated with steam in order to remove the last traces of solvent. It may also be isolated by distilling oil the solvent, if desired with the aid of a vacuum or of steam or both. The yield of the new product is almost quantitative. The resulting dyestufi' is a blue violet powder crystallizing from nitrobenzene in the form of fine needles. It dissolves in concentrated sulphuric acid with a blue red coloration and dyes cotton from a brown vat currant shades of excellent fastness.

Instead of the aforesaid dibro1no-3.4.8.9- dibenzopyrene-5.lO-quinone, an equivalent amount of the corresponding dichloroor diiodo-derivative may be used. The reaction may also be carried out in other solvents or suspension media than naphthalene, for example in nitrobenzene, or also in the ab sence of solvents or suspension media.

Example 2 41 parts of monobromo-3.4.8.9-dibenzopyrene-5.10-quinone are boiled, while stirring, in 400 parts of naphthalene with parts of alpha-aminoanthraquinone, parts of cal cined sodium carbonate and at parts of copper oxide, until the reaction product is practio H o I i (no cally free from bromine. The resulting dyestutl is worked up as described in example 1 and is a violet powder dissolving to a red solution in concentrated sulphuric acid and dyeing cotton from a blue red vat red-violet shades of excellent fastness.

What we claim is:

1. As new articles of manufacture, the vat dyestuffs corresponding to the general formula wherein n is 1 or 2, which dyestuffs dye cot ton strong currant to violet red shades of excellent fastness from brown red to blue red vats and dissolve to red to blue red solutions in concentrated sulphuric acid.

2. As new articles of manufacture, the vat which dye cotton from brown red vats strong currant shades of excellent fastness and dissolve in concentrated sulphuric acid to give blue red solutions.

3. As a new article of manufacture, the vat dyestuil probably corresponding to the formula which dyes cotton from a brown red vat strong currant shades of excellent fastness, dissolves to a blue red so ution -in concentrated sulphuric acid, and which is obtainable by condensing molecular proportions of alpha-amino-anthraquinone with 1 molecular proportion of the dibromo-3xl.8.9-dibenzopyrene-5.10-quinone which is obtainable by dissolving parts of pure 3.4.8.9-dibenzo pyrene-5.1()-quinone in 330 parts of chlorosulphonic acid, adding from 1.65 to 2.3 parts of iodine and then at room temperature 20 parts of bromine, and heating to from to C. until the bulk of the bromine has been taken up.

In testimony whereof we have hereunto set our hands.

MAX ALBERT KUN Z.

KARL KOEBERLE.

Certificate of Correction Patent No. 1,825,87 i. I Granted October 6, 1931, to MAX ALBERT KUNZ ET AL.

It is hereby certified that error appears in the printed specification of the abovenumbered patent requiring correction as follows: Page 2, claim 3, strike out the formula and insert instead qmz I @p i and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 26th day of January, A. D. 1932.

[SEAL] M. J. MOORE,

Acting aommz'ssz'oner of Patents. 

